CN100503431C

CN100503431C - Carbon-based material and method of producing the same and composite material and method of producing the same

Info

Publication number: CN100503431C
Application number: CNB2005100958276A
Authority: CN
Inventors: 曲尾章; 野口徹
Original assignee: Nissin Kogyo Co Ltd
Current assignee: Nissin Kogyo Co Ltd
Priority date: 2004-09-03
Filing date: 2005-09-02
Publication date: 2009-06-24
Anticipated expiration: 2025-09-02
Also published as: KR20060050973A; EP1632457A3; CN1743266A; EP1632457B1; US20060155009A1; JP4293957B2; EP1632457A2; KR100660401B1; US8182727B2; US20080139699A1; JP2006069865A

Abstract

A method of producing a carbon-based material includes steps (a), (b) and (c). In the step (a), an elastomer and at least a first carbon material is mixed and the first carbon material is dispersed by applying a shear force to obtain a composite elastomer. In the step (b), the composite elastomer is heat-treated to vaporize the elastomer, and a second carbon material is obtained. In the step (c) the second carbon material is heat-treated together with a substance including an element Y to vaporize the substance including the element Y, the melting point of the element Y being lower than the melting point of the first carbon material.

Description

Carbonaceous material and manufacture method thereof, matrix material and manufacture method thereof

Technical field

The present invention relates to carbonaceous material and manufacture method thereof, matrix material and manufacture method thereof.

Background technology

Use the matrix material of carbon materials such as carbon fiber, carbon black, graphite, carbon nanofiber extremely to gaze at (for example, with reference to patent documentation 1).Because such matrix material comprises carbon materials such as carbon nanofiber, improve electroconductibility, thermal conduction, physical strength etc. so can expect it.

But, carbon material usually and the wetting property (affinity) between the body material of matrix material low, the dispersiveness in body material is also low.In addition, particularly because carbon nanofiber has very strong coherency each other, so be difficult to make carbon nanofiber to be evenly dispersed in the base material of matrix material.Therefore, be difficult to obtain have the matrix material of the carbon nanofiber of desired characteristic now, and, carbon nanofiber with high costs can't efficiently be utilized.

Patent documentation 1: the spy opens flat 5-78110 communique

Summary of the invention

Therefore, the objective of the invention is to, a kind of infiltrating carbonaceous material and manufacture method thereof of improving the surface is provided.In addition, the present invention also aims to, a kind of matrix material and manufacture method thereof of homodisperse carbonaceous material is provided.

Manufacture method according to carbonaceous material of the present invention comprises: operation (a), and the mixed elastomer and at least the first carbon material, and utilize shearing force to disperse and the acquisition composite elastic body; Operation (b), the described composite elastic body of thermal treatment makes the elastomerics gasification that is included in this composite elastic body, obtains second carbon material; And operation (c), described second carbon material with melting point the material thermal treatment with element y lower than described first carbon material, is made the gasification substance with element y.

The operation of manufacturing method according to the invention (a), the free atom group that generates in the elastomerics of being cut off by shearing force attacks the surface of first carbon material, thereby the dispersiveness of elastomeric first carbon material is improved by sensitization in the surface of first carbon material therefore.In addition, when using carbon nanofiber as first carbon material, elastomeric unsaturated link(age) or group, the atomic group particularly terminal with the active part of carbon nanofiber combines, and reduces the cohesive force of carbon nanofiber, improves its dispersiveness.

And the operation of manufacturing method according to the invention (b) is owing to by thermal treatment gasification elastomerics, therefore, can obtain the surface by second carbon material of sensitization.And the operation of manufacturing method according to the invention (c) has the material of element y by thermal treatment gasification, and element y is attached to the surface of second carbon material, can obtain the carbonaceous material that the wetting property with body material improves.Therefore, the carbonaceous material that manufacturing method according to the invention obtains is easy to utilize in general metal processing for example in the processing of casting etc.

According to elastomerics of the present invention, can use rubber based elastomers or thermoplastic elastomer.In addition, if when using the rubber based elastomers, elastomerics can be crosslinked body or uncrosslinked body.As the raw material elastomerics,, use uncrosslinked body if when using the rubber based elastomers.

Make carbon material be dispersed in operation (a) in the elastomerics by shearing force, open type roller method, the mixing method of closed, the multiaxis that can adopt roller to be spaced apart smaller or equal to 0.5mm push mixing method etc.

According to carbonaceous material of the present invention, the surface of carbon material has first integrated structure and second integrated structure, described first integrated structure is in the structure that constitutes on the carbon atom of described carbon material in conjunction with element X, and described second integrated structure is in conjunction with the structure of element y on element X.

Manufacture method according to matrix material of the present invention comprises operation (d), and described carbonaceous material and body material that method according to claim 1 is obtained mix.

The surface of the carbonaceous material that obtains according to the present invention is owing to be attached with element y, therefore and the wetting property between the body material of matrix material good.Particularly, when the body material as matrix material uses aluminium or magnesium, use as element y if constitute the element of aluminium alloy or magnesium alloy, because the wetting property of body material and element y is good, therefore, the wetting property of carbonaceous material and body material is also good.In addition, by improving, the wetting property of carbonaceous material can be dispersed in carbonaceous material in the matrix metal material.

Description of drawings

Fig. 1 is the synoptic diagram of the mixing method of the elastomerics of the open type roller method used in the embodiment of the invention and carbonaceous material.

Fig. 2 is a structural representation of making the device of matrix material by non-pressurised osmose process.

Fig. 3 is a structural representation of making the device of matrix material by non-pressurised osmose process.

Fig. 4 is the figure that the XPS data of the carbonaceous material that obtains according to present embodiment are shown.

Fig. 5 is the figure that the EDS data (carbon) of the matrix material that obtains according to present embodiment are shown.

Fig. 6 is the figure that the EDS data (oxygen) of the matrix material that obtains according to present embodiment are shown.

Fig. 7 is the figure that the EDS data (magnesium) of the matrix material that obtains according to present embodiment are shown.

Embodiment

Below, with reference to accompanying drawing embodiments of the invention are elaborated.

The manufacture method of carbonaceous material involved in the present invention comprises: operation (a), and mixed elastomer, at least the first carbon material, and utilize shearing force to disperse and the acquisition composite elastic body; Operation (b), the thermal treatment composite elastic body makes the elastomerics gasification that is included in this composite elastic body, obtains second carbon material; And operation (c), second carbon material with melting point the material thermal treatment with element y lower than first carbon material, is made the gasification substance with element y.

The manufacture method of matrix material involved in the present invention can comprise: operation (d), above-mentioned carbonaceous material is mixed with the body material of matrix material.

(A) at first, elastomerics is described.

Elastomer molecular weight is preferably 5000 to 5,000,000, and more preferably 20,000 to 3,000,000.Because if elastomeric molecular weight is in this scope, the mutual complexing of elastomer molecules interconnects, so elastomerics invades the agglomerative carbon nanofiber each other easily, the effect of therefore separating carbon nanofiber is remarkable.When elastomeric molecular weight less than 5000 the time, elastomer molecules complexing fully mutually even if apply shearing force in the operation in the back, disperses the effect of first carbon material also less.In addition, when elastomeric molecular weight greater than 5,000,000 the time, elastomerics is too hard, processing is difficulty.

By adopting Hahn's echo method of PULSED NMR, elastomerics was preferably for 100 to 3000 μ seconds in the spin-spin relaxation time (T2n/30 ℃) of the network component of 30 ℃ of uncrosslinked bodies of measuring down, more preferably 200 to 1000 μ seconds.Because have the spin-spin relaxation time (T2n/30 ℃) of above-mentioned scope, so elastomerics can be very soft and be had a very high transport properties of molecules.Therefore, when the mixed elastomer and first carbon material, elastomerics can easily invade between the mutual slit of first carbon material by higher molecular motion.The spin-spin relaxation time (T2n/30 ℃), elastomerics just can not have sufficient transport properties of molecules if shorter second than 100 μ.In addition, the spin-spin relaxation time (T2n/30 ℃), it is easy to be mobile as liquid that elastomerics will become if longer second than 3000 μ, thereby be difficult to make the dispersion of first carbon material.

In addition, by adopting Hahn's echo method of PULSED NMR, elastomerics was preferably for 100 to 2000 μ seconds in the spin-spin relaxation time (T2n) of the network component of 30 ℃ of crosslinked bodies of measuring down.Its reason is identical with above-mentioned uncrosslinked body.That is, the uncrosslinked body with above-mentioned condition undertaken crosslinkedization by manufacture method of the present invention, and the T2n of the crosslinked body that obtains roughly is comprised in the above-mentioned scope.

By the spin-spin relaxation time that the Hahn's echo method that adopts PULSED NMR obtains, be the yardstick of the transport properties of molecules of expression material.Specifically, if the elastomeric spin-spin relaxation time is measured by the Hahn's echo method that adopts PULSED NMR, then can detect have relaxation time first composition of the first short spin-spin relaxation time (T2n), and have relaxation time second composition of the second long spin-spin relaxation time (T2nn).First composition is equivalent to high molecular network component (molecule of the skeleton), and second composition is equivalent to high molecular non-network component (compositions of branches and leaves such as terminal chain).And, we can say that the first spin-spin relaxation time, the short molecule mobility was low more more, elastomerics is hard more.In addition, the first spin-spin relaxation time, long more transport properties of molecules was high more, and elastomerics is soft more.

As the assay method among the impulse method NMR, not only can be Hahn's echo method, also can be suitable for three-dimensional echo method, CPMG method (Carr-Purcell-Meiboom-Gill method) or 90 ℃ of impulse methods.But because elastomerics involved in the present invention has the moderate spin-spin relaxation time (T2), Hahn's echo method is the most suitable.General three-dimensional echo method and 90 ℃ of impulse methods are suitable for measuring short T2, and Hahn's echo method is suitable for measuring moderate T2, and the CPMG method is suitable for measuring long T2.

At least one in main chain, side chain and terminal chain of elastomerics have to first carbon material particularly the atomic group of the end of carbon nanofiber have the unsaturated link(age) or the group of affinity, have these atomic groups of easy generation or the base character.Unsaturated link(age) or base are select from functional groups such as two keys, triple bond, α hydrogen, carbonyl, carboxyl, hydroxyl, amino, cyano group, ketone group, amide group, epoxy group(ing), ester group, vinyl, halogen, polyurethane-base, biuret groups, allophanate group, urea groups at least a.

Carbon nanofiber usually its side by the six-ring of carbon atom constitute, terminal five-ring and the closed structure of importing, still,,, on its part, generate atomic group or functional group easily so be easy to generate defective in the reality because there is structural unreasonable part.In the present embodiment, because at least one in elastomeric main chain, side chain and the terminal chain has high unsaturated link(age) or the group of atomic group affinity (reactivity or polarity) with carbon nanofiber, so can realize combining of elastomerics and carbon nanofiber.Thereby the cohesive force that can overcome carbon nanofiber makes it be easy to more disperse.And the mixing elastomerics and first carbon material be for example carbon nanofiber the time, and elastomeric molecular chain is cut off and defective that the free atom group that generates attacks carbon nanofiber, generates atomic group on the surface of carbon nanofiber.

As elastomerics, can use natural rubber (NR), epoxy natural rubber (ENR), styrene-butadiene rubber(SBR) (SBR), paracril (NBR), chloroprene rubber (CR), ethylene-propylene rubber(EPR) (EPR, EPDM), isoprene-isobutylene rubber (IIR), chlorobutyl rubber (CIIR), acrylic rubber (ACM), silicon rubber (Q), viton (FKM), divinyl rubber (BR), epoxidation divinyl rubber (EBR), epichloro hydrin rubber (CO, CEO), chemglaze (U), thiorubber elastomerics classes such as (T); Ethylene series (TPO), polyvinyl chloride system (TPVC), polyester system (TPEE), polyurethane system (TPU), polyamide-based (TPEA), polystyrene thermoplastic elastomers such as (SBS); And the mixture of these materials.Particularly, the preferred high elastomerics of polarity that easily generates free atom group elastomeric the time mixing that uses, for example, natural rubber (NR), paracril (NBR) etc.In addition, even the low elastomerics of polarity ethylene-propylene rubber(EPR) (EPDM) for example by mixing temperature being set at than higher temperature (for example under the situation of EPDM, 50 ℃～150 ℃), can generate atomic group, thereby can be used for the present invention.

The composite elastic body of present embodiment can be with crosslinked body elasticity body, uncrosslinked body elasticity body or thermoplastic elastomer directly as the elastic system material.

(B) below, first carbon material is described.

First carbon material can use carbon allotrope, for example can rein in the carbon etc. from carbon fiber, carbon black, amorphous carbon, graphite, diamond and richness and select.Here comprise carbon nanofiber in the said carbon fiber.Therefore carbon black, can utilize than being easier to owing to cheaply and at the upper reaches, market be connected with multiple rank.In addition, the carbon material of small material, for example nanofiber or rich nano material of reining in carbon etc. can obtain high reinforced effects with a spot of combined amount.

The use level that can set first carbon material according to the kind and the purposes of carbonaceous material.

Can use various raw-material various other carbon blacks of level of employing according to carbon black of the present invention.Can adopt its basic comprising particle (so-called primary particle) monomer or its heat bonding and bonded is called as the state of aggregate (so-called secondary aggregation body), but preferably use the material of the advanced structure of having of aggregate prosperity as reinforcing filler.

The carbon black that the present invention uses, basic comprising particulate median size is preferably smaller or equal to 100nm, more preferably smaller or equal to 50nm.The particle of carbon black is more little, and volume effect and reinforced effects are big more, but median size is preferably 10nm～30nm in the practical application.

In addition, the granular size of carbon black also can be represented with the nitrogen adsorption specific surface area, at this moment, " rubber is with carbon black-fundamental characteristics-second one: (the go system is with カ-ボ Application Block ラ Star Network-fundamental characteristics-the 2nd one: Bi Biao Mian Plot asks め side-stop up to the method for calculation-nitrogen adsorption method of specific surface area-one-point method with JIS:K6217-2 (2001)

The sorption method-

The point method) " nitrogen adsorption specific surface area (m ²/ g) measure, for more than or equal to 10m ²/ g is preferably more than and equals 40m ²/ g.

In addition, the carbon black that the present invention uses is subjected to the influence of height of the structure of the aggregate prosperity that its basic comprising particle heat bonding forms owing to reinforced effects, and therefore, the DBP absorbed dose is more than or equal to 50m ³/ 100g, be preferably more than and equal 100m ³During/100g, reinforced effects is big.This is because when the DBP absorbed dose is many, constitute the more flourishing structure of aggregate.

Be used for carbon black of the present invention, for example can use SAF-HS (N134, N121), SAF (N110, N115), ISAF-HS (N234), ISAF (N220, N220M), ISAF-LS (N219, N231), 1SAF-HS (N285, N229), HAF-HS (N339, N347), HAF (N330), HAF-LS (N326), T-HS (N351, N299), T-NS (N330T), MAF (N550M), FEF (N550), GPF (N660, N630, N650, N683), SRF-HS-HM (N762, N774), SRF-LM (N760M, N754, N772, N762), FT, HCC, HCF, MCC, MCF, LEF, MFF, RCF, ranks such as RCC, and TOKA carbon black, HS-500, acetylene black, electrical conductivity Carbon blacks such as KETJEN carbon black.

When first carbon material is a carbon fiber particularly carbon nanofiber the time, the composite elastic body of present embodiment preferably comprises the carbon nanofiber of 0.01～50 weight %.

The carbon nanofiber mean diameter is preferably 0.5 to 500nm, for the intensity that improves composite elastic body more preferably 0.5 to 30nm.And carbon nanofiber both can be that the fibers straight shape also can be the curved fiber shape.

Can enumerate so-called carbon nanotube etc. as carbon nanofiber.Carbon nanotube comprises that the graphite sheet of carbon hexagonal wire side is closed into single layer structure cylindraceous or these cylindrical structures are configured to canular multilayered structure.That is, carbon nanotube both can only be made of single layer structure, also can only be made of multilayered structure, can also comprise single layer structure and multilayered structure simultaneously.And, can also use part to comprise the carbon material of carbon nanotube structure.In addition, except that the such title of carbon nanotube, can also name with the such title of graphite protofibril nanotube.

Single-layer carbon nano-tube or multilayer carbon nanotube can be made desired size by arc discharge method, laser ablation method, vapour deposition process etc.

Arc discharge method is a kind ofly to carry out arc-over between the electrode materials made from carbon-point under subatmospheric slightly argon of pressure or hydrogen atmosphere, thereby obtains being piled up in the method for the multilayer carbon nanotube on the negative electrode.In addition, single-layer carbon nano-tube is from catalyzer such as mixed Ni/cobalts described carbon-point and after carrying out arc-over, is attached to obtain in the carbon black on the processing vessel medial surface.

The laser ablation method is a kind of in rare gas (for example argon), by making carbon surface fusion, evaporation to the intense pulse laser as the carbon surface irradiation YAG laser that is mixed with catalyzer such as nickel/cobalt of target, thereby obtains the method for single-layer carbon nano-tube.

Vapour deposition process is hydrocarbon polymers such as pyrolysis benzene, toluene in gas phase, and synthesizing carbon nanotubes more specifically, can be enumerated flowing catalyst method, Zeolite support catalyst method etc.

Carbon material carried out surface treatment in advance before mixing with elastomerics, for example, by carrying out ion implantation processing, sputter etching processing, plasma treatment etc., can improve and elastomeric binding property, wetting property.

(C) then, y describes to element.

The surface that element y is combined in second carbon material be used to improve carbonaceous material with the wetting property of body material.Usually, carbon material and the metallic substance for example wetting property of aluminium or magnesium are bad, but just can improve wetting property by the carbonaceous material that uses the surface to have element y.In addition, granular material with element y is blended in carries out pre-dispersedly in the elastomerics, when being blended in first carbon material in the elastomerics, can disperse first carbon material more well like this.At this moment, in operation (a), can in elastomerics, mix before first carbon material or and mix material simultaneously with element y with first carbon material.

Median size with material of element y is preferably greater than the mean diameter of employed first carbon material.In addition, the median size with material of element y is smaller or equal to 500 μ m, is preferably 1～300 μ m.In addition, the shape with material of element y is not limited only to form of spherical particles, so long as around the material with element y turbulent shape mobile shape takes place when mixing, can also be tabular, flakey.

As material with element y, be preferably melting point metal or the semi-metal lower than first carbon material, more preferably melting point is smaller or equal to 1000 ℃ low melting point (high vapour pressure) metal or semi-metal.Satisfy above-mentioned condition if having the melting point of the material of element y, can not damage carbon material in the thermal treatment of operation (c), just can gasify has the material of element y.

When carbonaceous material was mixed with the body material that is made of aluminium or magnesium, element y preferably comprised select at least a from magnesium, aluminium, silicon, calcium, titanium, vanadium, chromium, manganese, iron, nickel, copper, zinc, pick.Therefore, as material, can comprise at least a element y that from these elements, selects with element y.These elements use as the element that constitutes so-called aluminium alloy or magnesium alloy, combine with aluminium or magnesium easily, with aluminium or magnesium bonded state under stable existence, therefore preferred these elements of use.Particularly, as element y, the preferred magnesium good, zinc, the aluminium etc. of using with the associativity of aluminium that becomes body material or magnesium.Particularly, in the oxygen of surface bonding, preferably easy and oxygen bonded magnesium are used as element y as element X at first carbon material.Therefore, the carbonaceous material that obtains like this, have first integrated structure and second integrated structure on the surface of carbon material, first integrated structure is in the structure that constitutes on the carbon atom of carbon material in conjunction with element X, and second integrated structure is in conjunction with the structure of element y on element X.Particularly, when first integrated structure is on constituting the carbon atom of carbon material in the structure in conjunction with oxygen, above-mentioned second integrated structure preferably on oxygen in conjunction with the structure of magnesium.

At this, the material that will have element y has been described in operation (a) and the mixing situation of elastomerics, but has been not limited thereto, in operation (c), be in just passable as long as have the material of element y with the heat treated state of second carbon material.For example, in operation (c), also the material with element y can be placed in the heat treatment furnace with second carbon material, gasify by thermal treatment.At this moment, the material with element y can not be a particulate state.

In addition, comprise that at this aluminium or magnesium that becomes body material main component is the alloy of aluminium or magnesium.

(D) below, in elastomerics, mix carbon material, also describe by shearing force dispersive operation (a).

In above-mentioned elastomerics, make carbon material dispersive operation (a), can use open type roller method, the mixing method of closed, multiaxis to push mixing method etc. by shearing force.

In the present embodiment, as making the material with element y and first carbon material be blended in operation in the elastomerics, narrate having adopted roller to be spaced apart smaller or equal to the example of the open type roller method of 0.5mm.

Fig. 1 is to use the synoptic diagram of the open type roller method of two rollers.In Fig. 1, symbol 10 expressions first roller, symbol 20 expressions second roller.First roller 10 and second roller 20 with predetermined interval d, be preferably smaller or equal to 1.0mm, 0.1 to 0.5mm arranged spaced more preferably.First roller and second roller are rotated with forward or reverse.In illustrated example, first roller 10 and second roller 20 are pressed the direction rotation shown in the arrow.With the surface velocity of first roller 10 as V1, with the surface velocity of second roller 20 as V2, both surface velocities are preferably 1.05 to 3.00 than (V1/V2) so, more preferably 1.05 to 1.2.By using such surface velocity ratio, the shearing force that can obtain to expect.At first, under the state of first roller 10 and 20 rotations of second roller,, be formed on and accumulate elastomeric so-called bank (bank, storing institute) 32 between first roller 10 and second roller 20 to second roller, 20 coiling elastomericss 30.In this bank 32, add material, rotate first roller 10 and second roller 20 again, the operation of carrying out mixed elastomer 30 and having the material of element y with element y.Afterwards, to this elastomerics 30 and have in the mixed bank 32 of the material of element y and add first carbon material 40, rotate first roller 10 and second roller 20.And, the interval of first roller 10 and second roller 20 narrowed down and become above-mentioned interval d, under this state, with first roller 10 and second roller 20 with predetermined surface velocity than rotation.Like this, strong shear action can be separated from each other first carbon material that has condensed by this shearing force, thereby is dispersed in the elastomerics 30 in elastomerics 30 like one one ground extraction.In addition, the shearing force that produces by roller make be dispersed in the intravital material with element y of elasticity around flowing of turbulent shape taken place.First carbon material that flows by this complexity further is dispersed in the elastomerics 30.In addition, have in mixing before the material of element y, if earlier the elastomerics 30 and first carbon material 40 are mixed, the motion of elastomerics 30 will be limited by first carbon material 40, so, mix material and will become difficult with element y.Therefore, preferably in elastomerics 30, add the operation of implementing to mix material before first carbon material 40 with element y.

In addition, in operation (a), generate free atom group in the elastomerics of being cut off by shearing force, this free atom group attacks the surface of first carbon material, thereby the surface of first carbon material is by sensitization.For example, when elastomerics used natural rubber (NR), each natural rubber (NR) molecule was cut off when mixing in roller, and molecular weight ratio diminishes before putting into the open type roller.Generating in cut like this natural rubber (NR) molecule has atomic group, and atomic group is attacked the surface of first carbon material when mixing, thereby the surface of first carbon material is by sensitization.

In addition, in this operation (a), in order to obtain high as far as possible shearing force, the mixing of the elastomerics and first carbon material, preferably 0 to 50 ℃, more preferably under 5 to 30 ℃ lower temperature, carry out.When using open type roller method, the temperature of roller is preferably set to above-mentioned temperature.Even be set under the narrowest state also widely by interval d, can be advantageously implemented in the dispersion of first carbon material 40 in the elastomerics 30 than the median size of material with element y with first roller 10 and second roller 20.

At this moment, because the elastomerics of present embodiment has above-mentioned feature, be elastomeric molecular conformation (molecular length), molecular motion, with the features such as chemical interaction of carbon material, thereby can easily realize the dispersion of first carbon material, therefore, can obtain the good composite elastic body of dispersiveness and dispersion stabilization (first carbon material is difficult to condense once again).More particularly, when elastomerics is mixed with first carbon material, have the molecular length of appropriateness and the elastomerics of higher transport properties of molecules and invade carbon material each other, elastomeric specific part combines with the active high part of first carbon material by chemical interaction.In this state, if with the mixture of strong shear action in the elastomerics and first carbon material, be accompanied by elastomeric first carbon material that moves and also be moved, first carbon material that has condensed is separated, is dispersed in the elastomerics.In addition, this first pre-dispersed carbon material be by can preventing to condense once more with elastomeric chemical interaction, thereby has good dispersion stabilization.

In addition, owing to comprise the material with element y of predetermined amount in the elastomerics, by being created on elastomeric as the flowing of several bursts of complexity of turbulent flow around the material with element y, shearing force is also had an effect drawing back on the direction of each carbon material.Therefore, even diameter is about smaller or equal to the carbon nanofiber of 30nm or the carbon nanofiber of curved fiber shape,, therefore also can be evenly dispersed in the elastomerics owing to move to each flow direction by chemical interaction bonded elastomer molecules respectively.

Make first carbon material be dispersed in operation in the elastomerics by shearing force, have more than and be defined in above-mentioned open type roller method, also can adopt the mixing method of closed or the multiaxis of explanation in the above to push mixing method.In a word, so long as in this operation, it is just passable that elastomerics is applied the shearing force that can separate first carbon material that has condensed.

The material that has element y by above-mentioned making is dispersed in the elastomerics with first carbon material and mixes the composite elastic body that both mixed processes (mix, dispersion step) obtain, and can pass through the linking agent cross moulding, or not carry out crosslinked and moulding.The forming method of this moment for example can adopt mold pressing (compression) molding procedure or extrusion molding operation etc.The compression molding operation for example has following operation: will disperse to have the material of element y and the composite elastic body of first carbon material, and be placed in the forming mould that is set to certain temperature (for example being 175 ℃) with intended shape with the moulding of pressurized state process certain hour (for example being 20 minutes).

In the mixing of the elastomerics and first carbon material, dispersion step, perhaps in subsequent handling, can be added in the known additive that is adopted in the elastomeric processing such as rubber usually.For example can list as additive: linking agent, vulcanizing agent, vulcanization accelerator, vulcanization inhibitor, tenderizer, softening agent, stiffening agent, toughener, weighting agent, antiaging agent, tinting material etc.

(E) then, the composite elastic body that obtains by aforesaid method is described.

In the composite elastic body of present embodiment, first carbon material is evenly dispersed in the elastomerics as base material.This state also can be described as the state that elastomerics is being limited by first carbon material.In this state, not compared by the situation of first carbon material restriction, diminished by the mobility of the elastomer molecules of first carbon material restriction with elastomerics.Therefore, the first spin-spin relaxation time (T2n) of the composite elastic body that present embodiment is related, the second spin-spin relaxation time (T2nn) and spin-lattice relaxation time (T1), shorten than the monomeric situation of the elastomerics that does not comprise first carbon material.When particularly mixing first carbon material in the elastomerics that comprises the material with element y, compare with the elastomeric situation that comprises first carbon material, the second spin-spin relaxation time (T2nn) shortened.In addition, the spin-lattice relaxation time (T1) of linking agent changes pro rata with the combined amount of first carbon material.

In addition, under the state that elastomer molecules is limited by first carbon material,, can think that non-network component (non-mesh chain composition) reduces based on following reason.If promptly owing to first carbon material makes reducing of elastomeric transport properties of molecules globality, can think that based on underlying cause non-network component reduces: the part that non-network component can not easily move increases, and equal behavior takes place easy and network component; In addition, because non-network component (terminal chain) motion is easily adsorbed by the active centre of first carbon material easily so become.Therefore, compare with the monomeric situation of the elastomerics that does not comprise first carbon material, the composition branch rate (fnn) with composition of the second spin-spin relaxation time diminishes.Particularly compare with the elastomeric situation that comprises first carbon material, when mixing first carbon material in the elastomerics that comprises the material with element y, the composition branch rate (fnn) with composition of the second spin-spin relaxation time further diminishes.

Based on the above, the measured value that the related composite elastic body of present embodiment obtains by the Hahn's echo method that adopts PULSED NMR is preferably in following scope.

Promptly, in uncrosslinked body, be preferably for 100 to 3000 μ seconds in the first spin-spin relaxation time (T2n) of 150 ℃ of mensuration, second spin-spin relaxation time (T2nn) or do not exist or 1000 to 10000 μ seconds, and the composition branch rate (fnn) with composition of the second spin-spin relaxation time is less than 0.2.

The spin-lattice relaxation time (T1) that determines by the Hahn's echo method that adopts PULSED NMR be the same with the spin-spin relaxation time (T2) be the yardstick of the transport properties of molecules of expression material.Concrete we can say that the elastomeric spin-lattice relaxation time, the mobility of short molecule was low more more, elastomerics is hard more, and the mobility of long more molecule of spin-lattice relaxation time is high more, and elastomerics is soft more.

The composite elastic body that present embodiment is related, the yield temperature in the temperature dependency of dynamic viscoelastic is measured is preferably than the high temperature more than 20 ℃ of the monomeric yield temperature of raw material elastomerics.The composite elastic body of present embodiment, material and carbon material with element y very well are dispersed in the elastomerics.This state can be described as aforesaid elastomerics by the state of first carbon material restriction.Under this state, elastomerics is compared with the situation that does not comprise first carbon material, and its molecular motion diminishes, and the result is mobile the reduction.Owing to have such yield temperature characteristic, the temperature dependency of the dynamic viscoelastic of the composite elastic body of present embodiment diminishes, and the result can have good thermotolerance.

(F) then, the operation (b) to thermal treatment composite elastic body, manufacturing second carbon material describes.

Gasifying by the thermal treatment composite elastic body is included in elastomeric operation (b) in this composite elastic body, can be manufactured on material with element y around be dispersed with second carbon material of first carbon material.By this elastomeric operation (b) of gasification, be manufactured on operation (a) by second carbon material of sensitization.The surface of second carbon material, the free atom group by the elastomer molecules that is sheared in operation (a) is for example combined with the material with element y in operation (c) easily by sensitization.

Such thermal treatment can be selected various conditions according to the elastomeric kind of using, but is set at more than or equal to elastomeric gasification temperature and less than the gasification temperature of first carbon material to the heat treated temperature of major general.

Operation (b) is carried out in the presence of the material with element X, can obtain at second carbon material that constitutes on the carbon atom of first carbon material in conjunction with this element X.For example, composite elastic body comprises the material with element X, by the thermal treatment of operation (b), and can be in conjunction with this element X on the carbon atom that constitutes first carbon material.In addition, for example, operation (b) is carried out in the atmosphere that comprises the material with element X, can be in conjunction with this element X on the carbon atom that constitutes first carbon material.

Element X preferably can pass through the easy and carbon material bonded element of covalent linkage, and is light element, is preferably more than the divalent, for example can comprise select at least a from boron, nitrogen, oxygen, phosphorus.Element X is preferably oxygen or nitrogen.Particularly,, in the thermal treatment of operation (b), utilize easily, react easily with by the atomic group of first carbon material of sensitization, for example carbon nanofiber, thereby preferably use as element X because oxygen is present in the air.In addition, oxygen easily with other metallic substance for example magnesium etc. combine, can combine with metal or semimetallic element y easily in conjunction with second carbon material of oxygen.

When using oxygen,, when using nitrogen, need only that to carry out operation (b) in the atmosphere of ammonia just passable as element X as long as it is just passable to comprise oxygen in the heat treated atmosphere of operation (b) as element X.In addition, as element X the time, as long as carrying out operation (b) before, it is just passable to mix the material with element X in elastomerics with boron, phosphorus etc.At this moment, for example, when operation (a) mixing, can be mixed together material with element X.

According to the operation (b) of present embodiment, in heat treatment furnace, be placed on the composite elastic body that obtains in the operation (a), with the stove internal heating to gasifying for example 500 ℃ of elastomeric temperature.By heating, elastomerics is gasified, and is contacted by the element X that comprises in atmosphere in the surface of first carbon material of sensitization and the stove or the elastomerics in operation (a), can make surface treated second carbon material.Sensitization is rolled into a ball by the free atom of the elastomer molecules of shearing in the surface of second carbon material in operation (a), can with for example be present in that the oxygen in the atmosphere is easy in the stove combines.Like this second carbon material of Huo Deing surperficial oxidized, by sensitization, therefore, second carbon material can combine with metal or semimetallic element y easily.In addition, even without element X, the surface of second carbon material combines with element y easily by reacting by sensitization with elastomeric atomic group.

(G) then, to second carbon material and have the material thermal treatment together of element y, this operation (c) with material of element y that gasifies describes.

By second carbon material that will in operation (b), obtain with melting point than the low material thermal treatment of first carbon material and gasify that this has the operation (c) of the material of element y with element y, can make according to carbonaceous material of the present invention.

The thermal treatment temp of operation (c) is than the thermal treatment temp height of operation (b), be set at more than or equal to gasification have element y material temperature and less than the temperature of gasification first carbon material.In addition, the thermal treatment of operation (c), can be set at the temperature that has the material of element y more than or equal to gasification by thermal treatment temp with operation (b), (b) carries out simultaneously with operation, or also can carry out continuously with operation (b) the process of the thermal treatment temp that rises to operation (c) from room temperature.

Second carbon material that in operation (b), obtains and material with element y, temperature has the temperature of the material of element y in the heat treatment furnace more than or equal to gasification if be heated to, just gasification has the material of element y, element y is combined in the surface of second carbon material, or element y is combined in the element X with the surface bonding of second carbon material, can obtain according to carbonaceous material of the present invention.

And, have the material of element y, can be in operation (a) mixing and be pre-mixed in composite elastic body as mentioned above with elastomerics, also can be unmixed in composite elastic body.When in composite elastic body, not being pre-mixed material, can in the heat treatment furnace of operation (c), dispose material dividually with element y with second carbon material with element y.Element y by the thermal treatment gasification combines with the element X on the surface that is combined in second carbon material.In a word, in operation (c), by under the situation of wanting vaporized material to exist, placing second carbon material, the carbonaceous material that can obtain to expect with element y.

Vaporized like this element y combines the compound of generting element X and element y easily with the element X on the surface that is present in second carbon material.At this, element X can prevent element y and the direct combination of first carbon material.For example, when element y is aluminium, if the direct combination of first carbon material and aluminium just generates Al ₄C ₃Deng material easy and the water reaction, not preferred.Therefore, in the operation (c) of gasification element y before, preferably carry out element X is combined in the operation (b) on the surface of second carbon material.

The carbonaceous material of Huo Deing for example has the carbon atom that constitutes carbon nanofiber and combines with element X and element X and element y bonded structure in the surface of carbon nanofiber like this.Therefore, carbonaceous material for example has by the compound layer of carbon and element X (for example zone of oxidation) covering and by the structure of the reactant layer of element X and element y (for example magnesium) covering on the surface of carbon nanofiber.The surface tissue of this carbonaceous material can be analyzed (Energy Dispersive Spectrum) method by X line spectrum analysis (XPS) method or EDS and analyze.

(H) last, use the operation (d) of the matrix material of carbonaceous material to describe to acquisition.

In the operation in the present embodiment (d),, can obtain the matrix material of dispersed carbon material in the body material by mixing carbonaceous material and the body material that obtains in the above-described embodiments.

As body material, can be chosen in the metal that uses in the common casting processing, be preferably aluminium and alloy, magnesium and alloy thereof etc. as light metal.

Above-mentioned operation (d) for example can adopt following various forming methods.

(d-1: the powder compacting method)

The powder compacting operation of the matrix material of present embodiment, the operation of the carbonaceous material that can obtain in above-mentioned operation (c) by powder compacting is implemented.Particularly, for example with the carbonaceous material that obtains in the foregoing description with after body material mixes again, press at mould inner mould, under the sintering temperature (when for example body material is aluminium being 550 ℃) of body material, calcine, thereby can obtain matrix material.

Powder compacting in the present embodiment is identical with the moulding of metal forming processed powders, that is to say to comprise so-called metal-powder, in addition, uses powder stock, comprises in advance pre-mold pressing carbonaceous material and forms blocky raw material.And, except general sintering process, can also adopt the discharge plasma sintering method (SPS) of use plasma agglomeration device etc. as the powder compacting method.

In addition, carbonaceous material mixes with the particulate of body material, can adopt dry type mixing, wet mixing etc.Under the situation of wet mixing, the preferred powder mixes body material (wet mixing) of the carbonaceous material in solvent.When roughly keeping the profile of composite elastic body when combination between the element y, the bonding force between the element y is little, also pulverizes carbonaceous material easily.Therefore, when carrying out dry type mixing or wet mixing,, therefore, be easy to be used for metal processing owing to can use pulverized powder for example particulate state or fibrous carbonaceous material.

By the matrix material that such powder compacting produces, can obtain to make carbonaceous material to be dispersed in state in the body material.And the particle of the body material that uses in this operation (d) can be the material of containing element y, also can be the material of containing element y not.By adjusting the blending ratio of carbonaceous material and body material, can make the matrix material of rerum natura with expectation.

(d-2: castmethod)

The casting process of matrix material can be blended into body material by the carbonaceous material that the foregoing description obtains for example in the molten metal, and the operation of casting in having the mold of intended shape is implemented.This casting process can adopt and for example inject die casting method, casting die, the low pressure casting method that molten metal is implemented in the mold of steel.Can adopt utilizing thixo casting method that high-pressure trend makes its high pressure casting that solidifies, fused solution is stirred, utilizing centrifugal force that fused solution is cast centrifugal casting in the mold into etc. of the special casting classification that belongs to other in addition.In these castings, carbonaceous material is blended in the fused solution of body material, it is directly solidified in mold with this state, thereby make composite material forming.

The fused solution of the employed body material of casting process can be selected the employed metal of common casting processing, particularly from aluminium and alloy, magnesium and alloy thereof etc. as light metal, suitably selects monomer or its combination according to purposes.In addition,, just can improve the wetting property with element y, can also improve intensity as the matrix material of product if the metal that fused solution adopted is metal identical with the material with element y that is combined in carbonaceous material or the alloy that contains identical element y.In addition, by the blending ratio of adjustment, can make matrix material with expectation rerum natura for the carbonaceous material of the fused solution of body material.

(d-3: osmose process)

In the present embodiment, be penetrated in the carbonaceous material making fused solution with reference to Fig. 2 and Fig. 3, the operation that the non-pressurised osmose process of just so-called employing is cast describes.

Fig. 2 and Fig. 3 utilize non-pressurised osmose process to make the structural representation of the device of matrix material.The carbonaceous material that obtains in the foregoing description for example can use the carbonaceous material 4 of compression molding in advance in the forming mould of the shape with expectation.As shown in Figure 2, in airtight container 1, put into the carbonaceous material 4 (for example using the carbonaceous material of carbon nanofiber) of moulding as first carbon material 40.Above this carbonaceous material 4, place for example aluminium block 5 of body material piece.Then, by being built in heating unit not shown in the container 1, carbonaceous material 4 and the aluminium block 5 that is placed in the container 1 is heated to more than or equal to the aluminium fusing point.Fusion takes place aluminium block 5 after the heating becomes molten aluminum (molten metal).In addition, molten aluminum is penetrated into the vacancy in the carbonaceous material 4.

The carbonaceous material 4 of present embodiment has vacancy (space), and this vacancy can utilize capillary phenomenon that molten aluminum is permeated in integral body as soon as possible when compression molding in advance.In addition, if the shape that carbonaceous material 4 keeps to a certain degree just can not carried out compression molding in advance.Molten aluminum is penetrated into the inside of carbonaceous material 4, and soaks full fully.Then, stop the heating of the heating unit of container 1, make the molten metal cooling that is penetrated in the carbonaceous material 4, solidify, thus can make as shown in Figure 3 carbonaceous material 4 homodisperse matrix material 6.And, preferably adopt when making carbonaceous material 4 easily and molten metal bonded element y.

In addition, before heating container 1, reliever 2 that also can be by being connected container 1 for example vacuum pump is bled.And, can also from be connected on the container 1 rare gas element injection device 3 for example nitrogengas cylinder in container 1, import nitrogen.

And, in the present embodiment,, but be not limited to this with the shape of carbonaceous material compression molding in advance for expectation, can in having the mould of intended shape, place pulverized granular carbonaceous material, place the body material piece in the above, implement osmose process.

In addition, in the above-described embodiments non-pressurised osmose process is described, but so long as osmose process just is not limited thereto the pressurization osmose process that for example can use the pressure of the atmosphere by rare gas element etc. to pressurize.

As mentioned above, the surface of the carbonaceous material in the matrix material combines with element y, has improved the wetting property with carbonaceous material, fused solution for body material has sufficient wetting property, therefore, the whole ununiformity that reduces mechanical properties, the matrix material of acquisition homogeneous.

Embodiment

Below, embodiments of the invention are narrated, but the present invention is not limited to this.

(embodiment 1～3, comparative example 1)

(1) manufacturing of sample

(a) manufacturing of uncrosslinked sample (composite elastic body)

First operation: at roller directly is the polymer substance (100 weight parts (phr)) that adds the specified amount (100g) shown in the table 1 in 6 inches the open type roller (roll temperature is 10 to 20 ℃), and it is wound in the roller.

Second operation: the material with element y of the amount of Table 1 (weight part) is joined in the polymer substance.At this moment, roller is spaced apart 1.5mm.And, the kind of the material that adds of explanation below with element y.

The 3rd operation: then, first carbon material (being recited as " CNT " in the table 1) of the amount of Table 1 (volume %) is joined in the polymer substance that comprises the material with element y.At this moment, roller is spaced apart 1.5mm.

The 4th operation: after having added first carbon material, from roller, take out the mixture of the polymer substance and first carbon material.

The 5th operation: make roller be narrowed 0.3mm from 1.5mm at interval, add mixture, carry out thin-pass.At this moment, the surface velocity of two rollers ratio is 1.1.Carried out thin-pass repeatedly ten times.

The 6th operation: roller is set at predetermined interval (1.1mm) at interval, adds the mixture that carries out thin-pass, and take out.

Like this, obtain the uncrosslinked sample of the composite elastic body of embodiment 1～3.

And as the material with element y of embodiment 1～3, (median size is: 50 μ m) to use magnesium granules.In addition, the carbon material of first carbon material of embodiment 1～3 and comparative example 1 uses diameter (fiber footpath) to be about the carbon nanofiber (CNT) of 10～20nm.

(b) manufacturing of second carbon material

The uncrosslinked sample (composite elastic body) that obtains among above-mentioned (a) embodiment 1～3 is placed in the heat treatment furnace of nitrogen atmosphere, under temperature more than or equal to elastomeric gasification temperature (500 ℃), carry out 2 hours thermal treatment, make the elastomerics gasification, obtain second carbon material.

(c) manufacturing of carbonaceous material

Make second carbon material that obtains among above-mentioned (b) embodiment 1～3 directly in identical heat treatment furnace, under temperature more than or equal to the gasification temperature (570 ℃) of the material with element y (magnesium), carry out 1 hour thermal treatment, make gasification substance, obtain carbonaceous material with element y.

(s) manufacturing of matrix material

Be blended in powder 10g, the aluminium powder body 500g of the carbonaceous material that obtains among the embodiment 1～3 of above-mentioned (c) with ball mill, obtain powder mix.With the big or small compression molding of the powder mix that obtains like this with 30 * 40 * 20nm.Placement purity is 99.85% aluminium block on these moulding product, is placed in the heat treatment furnace of nitrogen atmosphere.This heat treatment furnace is heated to 750 ℃, and aluminium block generation fusion makes its inside that infiltrates into the compression molding product, obtains matrix material.The content of the carbon nanofiber in this matrix material is 1.6vol%.And it is that 99.85% median size is the particle of 28 μ m that the aluminium powder body uses purity.

And, as a comparative example 1, with ball mill mixing carbon nanofiber and aluminium powder body,, obtain the matrix material of comparative example 1 with identical method osmotic aluminium.

(2) mensuration of employing PULSED NMR

For each uncrosslinked sample, measure by the Hahn's echo method that adopts PULSED NMR.This mensuration is to adopt " JMN-MU25 " of NEC (strain) system to carry out.Mensuration is to be at observing nuclear ¹H, resonant frequency are 25MHz, carry out under the condition that 90 ° of pulse widths are 2 μ sec, the pulse sequence (90 ° of x-Pi-180 ° of x) by Hahn technique thus Pi is carried out various variations measures attenuation curves.In addition, sample is to insert sample tube to measure to the proper range in magnetic field.Measuring temperature is 150 ℃.Utilize this mensuration to obtain the first spin-spin relaxation time (T2n) of the uncrosslinked sample of raw material elastomerics monomer and matrix material, the second spin-spin relaxation time (T2nn), have the composition branch rate (fnn) of the composition of the second spin-spin relaxation time.Obtaining measuring temperature in addition is under 30 ℃ the situation, the monomeric first spin-spin relaxation time (T2n) of raw material elastomerics.Measurement result is as shown in table 1.Do not detect the second spin-spin relaxation time (T2nn) among the embodiment 1～3.Therefore, the composition branch rate (fnn) with composition of the second spin-spin relaxation time is 0 (zero).

(3) mensuration of yield temperature

For the uncrosslinked sample of raw material elastomerics monomer and composite elastic body, carried out the mensuration of yield temperature by Measurement of Dynamic Viscoelasticity (JIS K 6394).Particularly, yield temperature gives sinusoidal vibration (smaller or equal to ± 0.1%) for the sample of wide 5mm, long 40mm, thick 1mm, obtains the stress and the phasic difference δ that take place thus.At this moment, temperature is increased to 150 ℃ from-70 ℃ of beginnings with 2 ℃/minute heat-up rate.Its result represents in table 1.In table 1,150 ℃ of situations of not finding the flow phenomenon of sample are recited as " more than or equal to 150 ℃ ".

(4) analysis of the carbonaceous material by XPS analysis

Table 1 shows the carbonaceous material of the embodiment 1～3 that obtains in above-mentioned (c), the carbon nanofiber of comparative example 1 is carried out the result of XPS analysis.In table 1, when there is the bonded of carbon and oxygen in affirmation on the surface of carbonaceous material, be recited as " surface oxidation ", when not confirming the bonded of carbon and oxygen, be recited as " nothing ".In addition, Fig. 4 shows the synoptic diagram of XPS data of the carbonaceous material of embodiment 1.Two keys of first line segment, 50 expression C=O, the singly-bound of second line segment, 60 expression C-O, the combination between the 3rd line segment 70 expression carbon.

(5) analysis of the carbonaceous material of analyzing by EDS

The carbon nanofiber that table 1 shows the matrix material of the embodiment 1～3 that obtains in above-mentioned (d), comparative example 1 carries out the result that EDS analyzes.In table 1, confirm when having magnesium around the carbonaceous material, to be recited as " Mg is arranged ", when not confirming magnesium, be recited as " nothing ".In addition, Fig. 5, Fig. 6, Fig. 7 show the synoptic diagram of EDS data of the carbonaceous material of embodiment 1.Fig. 5～Fig. 7 carries out the view data that EDS analyzes, owing to be difficult to explanation with black white image, has therefore carried out positive and negative counter-rotating processing etc.Black part among Fig. 5 is divided expression carbon, promptly represents the existence as the carbon nanofiber of first carbon material.Black part among Fig. 6 is divided the existence of expression oxygen.Black among Fig. 7 (color is dark) part is represented the existence of magnesium.

(6) mensuration of the compressive strength of matrix material (compression endurance)

For the matrix material of the embodiment 1～3 that obtains in above-mentioned (d) and the matrix material of comparative example 1, having measured thickness is the test film of 10 * 10mm of 5mm 0.2% intensity (endurance) (σ 0.2) when compressing with 0.01mm/min.Maximum value, minimum value and the mean value (MPa) of compressive strength have been measured.Its result represents in table 1.

According to embodiments of the invention 1～3, from table 1, can confirm the following fact.Promptly comprise the material with element y and the spin-spin relaxation time (T2n and T2nn/150 ℃) of uncrosslinked sample (composite elastic body) under 150 ℃ of first carbon material, and do not comprise the material with element y and the raw material elastomerics of carbonaceous material and compare and to lack.In addition, comprise the material with element y and first carbon material uncrosslinked sample (composite elastic body) composition branch rate (fnn/150 ℃) with do not comprise the material with element y and the raw material elastomerics of carbonaceous material and compare little.From these data as can be seen first carbon material be dispersed in well the related composite elastic body of embodiment.

And, comprise the yield temperature of the uncrosslinked sample (composite elastic body) of the material with element y and first carbon material, to compare highly more than 20 ℃ with the raw material elastomerics, the temperature dependency of dynamic viscoelastic is little, has good thermotolerance.

From the XPS analysis result of the carbonaceous material of embodiment 1～3 as can be known, second carbon material is surperficial oxidized.

From the EDS analytical results of the carbonaceous material of embodiment 1～3 as can be known, around carbonaceous material, there are oxygen and magnesium.

The compressive strength of the combined shaping product of embodiment 1～3 is compared with the compressive strength of the matrix material of comparative example 1, and minimum value and maximum value significantly increase.In addition, the combined shaping product of embodiment 1～3 for the ununiformity of the maximum value of the mean value of compressive strength and minimum value ± 5%, and the ununiformity of the compressive strength of the matrix material of comparative example 1 is ± 50%.Therefore, the matrix material integral body of embodiment 1～3 is homogenized.

The carbonaceous material of embodiment 1～3 is evenly dispersed in the aluminium as body material, has obtained the whole matrix material that is homogenized.In addition, by significantly improving compressive strength, improve the wetting property between carbonaceous material and the aluminium.

The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Symbol description

1 container

2 decompressors

3 injection devices

4 carbon-based materials

5 aluminium blocks

6 composites

10 first rollers

20 second rollers

30 elastomericss

40 first carbon materials

Y has the material of element y

Claims

1. the manufacture method of a carbonaceous material comprises:

Operation (a), the mixed elastomer and at least the first carbon material, and utilize shearing force to disperse and the acquisition composite elastic body;

Operation (b), the described composite elastic body of thermal treatment makes the elastomerics gasification that is included in the described composite elastic body, obtains second carbon material; And

Operation (c) with melting point the material thermal treatment with element y lower than described first carbon material, makes the gasification substance with element y with described second carbon material;

Wherein said operation (b) is carried out in the atmosphere that comprises the material with element X, is constituting on the carbon atom of described first carbon material in conjunction with described element X; Described element X is select from boron, nitrogen, oxygen, phosphorus at least a;

Described material with element y comprises at least a element y that selects from magnesium, aluminium, silicon, calcium, titanium, vanadium, chromium, manganese, iron, nickel, copper, zinc;

Described first carbon material is at least one carbon allotrope of selecting from carbon fiber, amorphous carbon, graphite, diamond and soccerballene.

2. the manufacture method of carbonaceous material according to claim 1, wherein:

Described element X is oxygen or nitrogen.

3. the manufacture method of carbonaceous material according to claim 1, wherein:

Described composite elastic body is the material with described element y.

4. the manufacture method of carbonaceous material according to claim 1, wherein:

In described operation (c), described material with element y is placed in the heat treatment furnace with described second carbon material, and is gasified by thermal treatment.

5. the manufacture method of carbonaceous material according to claim 1, wherein:

Described carbonaceous material is the material that is blended in the body material that is made of aluminium.

6. the manufacture method of carbonaceous material according to claim 1, wherein:

Described carbonaceous material is the material that is blended in the body material that is made of magnesium.

7. the manufacture method of carbonaceous material according to claim 1, wherein:

Described material with element y is the material with any element y in magnesium, zinc, the aluminium.

8. the manufacture method of carbonaceous material according to claim 1, wherein:

Described first carbon material is a carbon black.

9. the manufacture method of carbonaceous material according to claim 1, wherein:

Described first carbon material is a carbon fiber.

10. the manufacture method of carbonaceous material according to claim 9, wherein:

Described carbon fiber is a carbon nanofiber.

11. the manufacture method of carbonaceous material according to claim 10, wherein:

The mean diameter of described carbon nanofiber is 0.5 to 500nm.

12. the manufacture method of carbonaceous material according to claim 1, wherein:

The described elastomeric molecular weight that uses in described operation (a) is 5000 to 5,000,000.

13. the manufacture method of carbonaceous material according to claim 1, wherein:

At least one in main chain, side chain and terminal chain of described elastomerics of using in described operation (a) has at least a unsaturated link(age) or the group of selecting that has affinity for carbon nanofiber from two keys, triple bond carbonyl, carboxyl, hydroxyl, amino, cyano group, ketone group, amide group, epoxy group(ing), ester group, halogen, polyurethane-base, biuret groups, allophanate group, urea/ureido functional base.

14. the manufacture method of carbonaceous material according to claim 1, wherein:

By the Hahn's echo method that adopts PULSED NMR the described elastomerics that uses in described operation (a) is measured, the spin-spin relaxation time T 2n of the described elastomerics that uses in described operation (a) network component of the uncrosslinked bodies of mensuration under 30 ℃ was 100 to 3000 μ seconds.

15. the manufacture method of carbonaceous material according to claim 1, wherein:

By the Hahn's echo method that adopts PULSED NMR the described elastomerics that uses in described operation (a) is measured, the spin-spin relaxation time T 2n of the described elastomerics that uses in described operation (a) network component of the crosslinked bodies of mensuration under 30 ℃ was 100 to 2000 μ seconds.

16. the manufacture method of carbonaceous material according to claim 1, wherein:

The described elastomerics that uses in described operation (a) is natural rubber or paracril.

17. the manufacture method of carbonaceous material according to claim 1, wherein:

Described operation (a) employing roller is spaced apart smaller or equal to the open type roller method of 0.5mm and mixes described elastomerics and described at least first carbon material, and utilizes shearing force to disperse.

18. the manufacture method of carbonaceous material according to claim 17, wherein:

In described open type roller method, the surface velocity ratio of two rollers is 1.05 to 3.00.

19. the manufacture method of carbonaceous material according to claim 1, wherein:

Described operation (a) is mixed described elastomerics and described at least first carbon material by the mixing method of closed, and utilizes shearing force to disperse.

20. the manufacture method of carbonaceous material according to claim 1, wherein:

Described operation (a) is pushed mixing method by multiaxis and is mixed described elastomerics and described at least first carbon material, and utilizes shearing force to disperse.

21. the manufacture method of carbonaceous material according to claim 1, wherein:

Described operation (a) is carried out under 0 ℃ to 50 ℃.